NO329326B1 - Process for the preparation of furfural from lignosulfonate waste liquid - Google Patents
Process for the preparation of furfural from lignosulfonate waste liquid Download PDFInfo
- Publication number
- NO329326B1 NO329326B1 NO20015031A NO20015031A NO329326B1 NO 329326 B1 NO329326 B1 NO 329326B1 NO 20015031 A NO20015031 A NO 20015031A NO 20015031 A NO20015031 A NO 20015031A NO 329326 B1 NO329326 B1 NO 329326B1
- Authority
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- Norway
- Prior art keywords
- furfural
- liquid
- heat source
- additional heat
- pentose
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- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000007788 liquid Substances 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 20
- 229920001732 Lignosulfonate Polymers 0.000 title claims abstract description 15
- 239000002699 waste material Substances 0.000 title claims abstract description 11
- 150000002972 pentoses Chemical class 0.000 claims abstract description 18
- 238000009835 boiling Methods 0.000 claims abstract description 13
- 239000007789 gas Substances 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 239000012071 phase Substances 0.000 claims abstract description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052753 mercury Inorganic materials 0.000 claims abstract description 3
- 239000012808 vapor phase Substances 0.000 claims description 8
- 230000006837 decompression Effects 0.000 claims description 4
- 239000000567 combustion gas Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000005325 percolation Methods 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 239000004117 Lignosulphonate Substances 0.000 abstract 2
- 235000019357 lignosulphonate Nutrition 0.000 abstract 2
- 239000007792 gaseous phase Substances 0.000 abstract 1
- 238000012423 maintenance Methods 0.000 abstract 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 235000011132 calcium sulphate Nutrition 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000001175 calcium sulphate Substances 0.000 description 2
- 239000008246 gaseous mixture Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000010793 Steam injection (oil industry) Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- -1 hydrogen ions Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
- C07D307/48—Furfural
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Furan Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Paper (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
Denne oppfinnelsen vedrører fremstillingen av furfural fra lignosulfonatspillvæske. This invention relates to the production of furfural from lignosulfonate waste liquid.
Avhengig av hvilken type tre som skal foredles, resulterer sulfittoppsluttingsprosessen i en spillvæske som kan inneholde fra 0,9 til 5,6% pentose som gjør dette til en kandidat for fremstilling av furfural. Depending on the type of wood to be processed, the sulfite impregnation process results in a waste liquid that can contain from 0.9 to 5.6% pentose, making it a candidate for the production of furfural.
Konvensjonelt fortykkes spillvæsken til et faststofflnnhold på 50% eller fullstendig tørt, og væsken eller det faste stoffet selges som lignosulfat. Pentose er en uønsket bestanddel i denne væsken. Conventionally, the waste liquid is thickened to a solids content of 50% or completely dry, and the liquid or solid is sold as lignosulphate. Pentose is an undesirable component in this liquid.
Spillvæsken fra prosessen mettes med kalsiumsulfat, slik at den høye temperaturen som er nødvendig for furfuralfremstilling (foretrukket over 200°C) resulterer i den hurtige og harde avsetningen av kalsiumsulfat på de oppvarmede overflatene, hvilket gjør videre kontinuerlig drift umulig. The waste liquid from the process is saturated with calcium sulphate, so that the high temperature required for furfural production (preferably above 200°C) results in the rapid and hard deposition of calcium sulphate on the heated surfaces, which makes further continuous operation impossible.
Dersom varmevekslere unngås ved substitusjon av direkte damptilførsel, er det ikke mulig å termodynamisk holde væsken i en kokende tilstand under dens oppholdstid på grunn av at substansene i løsning hever kokepunktet. Således er kokepunktet for væsken høyere enn kondensasjonspunktet for damp ved ethvert trykk. Som en konsekvens av dette forblir furfural fremstilt fra pentosen, midlertidig oppløst i væskefasen hvor, under den katalytiske effekten av væskens naturlige surhet, furfural kan reagere med pentose, eller lignosulfonatet, og med seg selv, hvilket således medfører store tap og derved dårlige utbytter. If heat exchangers are avoided by substitution of direct steam supply, it is not possible to thermodynamically keep the liquid in a boiling state during its residence time because the substances in solution raise the boiling point. Thus, the boiling point of the liquid is higher than the condensation point of the vapor at any pressure. As a consequence of this, furfural produced from the pentose remains temporarily dissolved in the liquid phase where, under the catalytic effect of the liquid's natural acidity, furfural can react with the pentose, or the lignosulfonate, and with itself, thus causing large losses and thereby poor yields.
US 2845441 A, FR 1129139 A og EP 0124507 B2 beskriver fremgangsmåter til fremstilling av furfural fra lignosulfonatspillvæske, der lignosulfonatspillvæsken varmes ved direkte dampinjeksjon og en furfuralrik dampfase kondenseres til å gi furfural. US 2845441 A, FR 1129139 A and EP 0124507 B2 describe methods for producing furfural from lignosulfonate waste liquid, where the lignosulfonate waste liquid is heated by direct steam injection and a furfural-rich vapor phase is condensed to give furfural.
Det er et formål ved den foreliggende oppfinnelsen å frembringe en fremgangsmåte for effektiv fremstilling av furfural fra lignosulfonatvæsker. It is an aim of the present invention to produce a method for the efficient production of furfural from lignosulfonate liquids.
Ifølge oppfinnelsen tilveiebringes en fremgangsmåte til fremstilling av furfural fra lignosulfonatspillvæske som inneholder pentose kjennetegnet ved at væsken holdes ved dens kokepunkt ved hjelp av en tilleggsvarmekilde og kontrollert dekompresjon i en tilstrekkelig tid for å omdanne pentosen til furfural som øyeblikkelig bringes over i dampfase når det dannes, og å separere den furfuralrike dampfasen fra vaskefasen uten at furfuralen reagerer med pentose, lingosulfat eller seg selv. According to the invention, a method for the production of furfural from lignosulfonate waste liquid containing pentose is provided, characterized in that the liquid is kept at its boiling point by means of an additional heat source and controlled decompression for a sufficient time to convert the pentose into furfural which is immediately transferred to the vapor phase when it is formed, and to separate the furfural-rich vapor phase from the wash phase without the furfural reacting with pentose, lingosulfate or itself.
Fremgangsmåten kan utføres i en reaktor som kan være en batchvis eller kontinuerlig reaktor. The method can be carried out in a reactor which can be a batch or continuous reactor.
Ved en foretrukket batch-fremgangsmåte varmes en lignosulfonatvæske ved damp i en reaktor som kontinuerlig trykkavlastes til trykk som er tilstrekkelig til å opprettholde koking av væsken, furfuralet som er dannet migrerer til dampfasen og fjernes med kondensatet og utvinnes. In a preferred batch process, a lignosulfonate liquid is heated by steam in a continuously depressurized reactor to a pressure sufficient to maintain boiling of the liquid, the furfural formed migrates to the vapor phase and is removed with the condensate and recovered.
I en kontinuerlig fremgangsmåte ifølge oppfinnelsen kokes væsken i en kontinuerlig reaktor ved hjelp av en tilleggsvarmekilde, væsken fjernes mens furfuralet som dannes i det vesentlige øyeblikkelig og fullstendig bringes over i gassfasen som forlater reaktoren og hvorfra det separeres. In a continuous method according to the invention, the liquid is boiled in a continuous reactor with the help of an additional heat source, the liquid is removed while the furfural that is formed is essentially instantly and completely transferred into the gas phase that leaves the reactor and from which it is separated.
Ved en form av oppfinnelsen varmes væsken i reaktoren ved hjelp av en tilleggsvarmekilde, væsken fjernes mens furfuralet som er dannet i det alt vesentlige øyeblikkelig og fullstendig bringes over i gassfasen hvorfra det separeres. In one form of the invention, the liquid in the reactor is heated by means of an additional heat source, the liquid is removed while the furfural that is formed is essentially immediately and completely transferred into the gas phase from which it is separated.
Tilleggsvarmekilden er foretrukket oppvarmet luft under trykk og dette kan tilføres ved et lavt nivå i reaktoren. Luften siver gjennom væsken i reaktoren, og ved å avgi sin varme holder den væsken i en kokende tilstand før den forlater reaktoren. The additional heat source is preferably heated air under pressure and this can be supplied at a low level in the reactor. The air seeps through the liquid in the reactor, and by giving off its heat, it keeps the liquid in a boiling state before it leaves the reactor.
Væsken tilføres foretrukket til reaktoren ved en temperatur mellom 180 og 280°C. The liquid is preferably supplied to the reactor at a temperature between 180 and 280°C.
Et kontrollert kretsløp kan frembringes for å holde trykket i toppen av reaktoren på en verdi som er svakt under trykket for den tilførte væsken. På denne måten forårsaker den resulterende frigjørende dampen at væsken gjennomgår en mindre trykksenking til en lavere temperatur som tvinger furfuralet over i dampfase, mens den oppvarmede luften opprettholder en kokende tilstand for væsken gjennom hele reaktoren. Således blir furfuralet som fremstilles fra pentosen øyeblikkelig og fullstendig fordampet ved sin dannelse; og forenes med luften og noe fordampet vann til å danne en gassaktig blanding med minimum utbyttetap av furfural, fordi reaksjoner mellom furfural og pentose på den ene siden, og med lignosulfonater på den andre siden ikke kan foregå på grunn av at pentosen og lignosulfonatene er igjen i løsningen. Reaksjonen av furfural med seg selv unngås ved fraværet av hydrogenioner i dampfasen. A controlled circuit can be provided to maintain the pressure at the top of the reactor at a value slightly below the pressure of the supplied liquid. In this way, the resulting freeing vapor causes the liquid to undergo a minor depressurization to a lower temperature that forces the furfural into the vapor phase, while the heated air maintains a boiling condition for the liquid throughout the reactor. Thus the furfural produced from the pentose is instantly and completely vaporized on its formation; and combines with the air and some evaporated water to form a gaseous mixture with minimum yield loss of furfural, because reactions between furfural and pentose on the one hand, and with lignosulfonates on the other hand cannot take place due to the fact that the pentose and lignosulfonates remain in the solution. The reaction of furfural with itself is avoided by the absence of hydrogen ions in the vapor phase.
Oppholdstiden i reaktoren er valgt slik at fullstendig omdannelse av pentosen oppnås. Ingen tilsetning av syre er nødvendig på grunn av den naturlige surheten av væsken som bevirker en tilstrekkelig sterk katalyse. The residence time in the reactor is chosen so that complete conversion of the pentose is achieved. No addition of acid is necessary due to the natural acidity of the liquid which causes a sufficiently strong catalysis.
Ingen varmevekslere er nødvendige, og derved unngås problemene forbundet med kalsiumsulfat, som diskutert over. No heat exchangers are required, thereby avoiding the problems associated with calcium sulfate, as discussed above.
Istedenfor å benytte oppvarmet luft som tilleggsvarmekilden kan andre egnede oppvarmede gasser eller gassblandinger (slik som varm forbrenningsgass) eller varmt kvikksølv benyttes, hvor alle disse lett separeres fra væsken ved slutten av reaksjonen. Instead of using heated air as the additional heat source, other suitable heated gases or gas mixtures (such as hot combustion gas) or hot mercury can be used, all of which are easily separated from the liquid at the end of the reaction.
Det vil forstås at varmen som er nødvendig ved tilleggsvarmemiddelet er relativt liten, da hovedsakelig alt som er nødvendig av dette er å fordampe furfuralet som fremstilles. Den lave varmen av fordampning av furfural, spesielt ved høye temperaturer, sikrer et lavt tilleggsvarmebehov. It will be understood that the heat required by the additional heating agent is relatively small, as essentially all that is required of this is to vaporize the furfural that is produced. The low heat of vaporization of furfural, especially at high temperatures, ensures a low additional heat requirement.
Utbyttet av furfural øker med den økende temperaturen i reaktoren mens tapene forårsaket av reaksjoner med pentose og lignosulfonater, så vel som bisulfltter minkes ved høyere temperaturer grunnet entropieffekten av alle aggregeringsreaksjoner. The yield of furfural increases with the increasing temperature in the reactor, while the losses caused by reactions with pentose and lignosulfonates, as well as bisulfites, decrease at higher temperatures due to the entropy effect of all aggregation reactions.
Det vil forstås at det ikke er nødvendig å tilsette noen syre til væsken for katalyse, da den naturlige surheten i væsken bevirker en tilstrekkelig sterk katalyse. It will be understood that it is not necessary to add any acid to the liquid for catalysis, as the natural acidity of the liquid causes sufficiently strong catalysis.
Fremgangsmåten ifølge oppfinnelsen er beskrevet nedenfor med referanse til det vedlagte flytdiagrammet. The method according to the invention is described below with reference to the attached flow chart.
En pumpe 1 tilfører en lignosulfonatspillvæske gjennom en in-line blander 2, der damp-tilførsel varmer den til en temperatur mellom 180 og 280°C, som således hever trykket tilsvarende. Ved hjelp av en strupeventil 3, underkastes væsken en mindre trykk-reduksjon i toppen av en termisk isolert søyleformet reaktor 4, og strømmer deretter nedover for å forlate reaktoren i bunnen via en syklon 5, hvilket resulterer i dekompresjon, avkjøling og fortykning. A pump 1 supplies a lignosulfonate waste liquid through an in-line mixer 2, where steam supply heats it to a temperature between 180 and 280°C, which thus raises the pressure accordingly. By means of a throttle valve 3, the liquid is subjected to a minor pressure reduction at the top of a thermally insulated columnar reactor 4, and then flows downwards to leave the reactor at the bottom via a cyclone 5, resulting in decompression, cooling and thickening.
Komprimert luft varmes elektrisk i en varmeveksler og denne tilføres via kontroll-kretsløp 7 i bunnen av reaktoren. Den varme luften siver oppover, og avgir sin varme til væsken og holder derved væsken i en kokende tilstand før den forlater toppen av reaktoren via et kontroUkretsløp 8, en kondensator 9 og en atmosfærisk absorpsjons-kolonne 10 utstyrt med en sirkulasjonspumpe 11. Compressed air is heated electrically in a heat exchanger and this is supplied via control circuit 7 at the bottom of the reactor. The hot air seeps upwards and gives off its heat to the liquid, thereby keeping the liquid in a boiling state before leaving the top of the reactor via a control circuit 8, a condenser 9 and an atmospheric absorption column 10 equipped with a circulation pump 11.
Kontrollkretsløpet holder trykket i toppen av reaktoren ved en verdi som er svakt under trykket til den innkommende væsken, slik at væsken i frigjørende damp gjennomgår en mindre trykksenking til en noe lavere temperatur mens den varme luften som tilføres i bunnen sikrer kontinuerlig koking av væsken i hele reaktoren. Furfuralet som er dannet fordampes øyeblikkelig og fullstendig og forenes med luften og dampen for å danne en gassaktig blanding som kondenseres i 9 og deretter samles opp i tank 12. Små mengder furfural som er trukket ut med luft gjenvinnes i absorpsjonskolonnen og samles opp i The control circuit keeps the pressure at the top of the reactor at a value that is slightly below the pressure of the incoming liquid, so that the liquid in releasing steam undergoes a minor pressure drop to a slightly lower temperature, while the hot air supplied at the bottom ensures continuous boiling of the liquid throughout the reactor. The furfural that is formed is instantly and completely vaporized and combines with the air and steam to form a gaseous mixture that is condensed in 9 and then collected in tank 12. Small amounts of furfural that have been drawn off with air are recovered in the absorption column and collected in
tank 12. tank 12.
Tilførselshastigheten av væsken og dimensjonene av reaktoren velges for å tilpasse en forhåndsbestemt oppholdstid av væsken i reaktoren. The feed rate of the liquid and the dimensions of the reactor are chosen to accommodate a predetermined residence time of the liquid in the reactor.
Claims (9)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19917178A DE19917178A1 (en) | 1999-04-16 | 1999-04-16 | Production of furfural from sulfite waste liquor involves heating by direct injection of steam, reaction by boiling under pressure, using easily separated ancillary, and complete vaporization by cooling and depressurization |
| PCT/ZA2000/000072 WO2000063488A1 (en) | 1999-04-16 | 2000-04-14 | Process for the production of furfural from lignosulphonate waste liquor |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| NO20015031D0 NO20015031D0 (en) | 2001-10-16 |
| NO20015031L NO20015031L (en) | 2001-12-11 |
| NO329326B1 true NO329326B1 (en) | 2010-09-27 |
Family
ID=7904762
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO20015031A NO329326B1 (en) | 1999-04-16 | 2001-10-16 | Process for the preparation of furfural from lignosulfonate waste liquid |
Country Status (13)
| Country | Link |
|---|---|
| US (1) | US6642396B1 (en) |
| EP (1) | EP1171665B1 (en) |
| AT (1) | ATE404728T1 (en) |
| AU (1) | AU5499900A (en) |
| BR (1) | BR0009815B1 (en) |
| CA (1) | CA2370561C (en) |
| DE (2) | DE19917178A1 (en) |
| DK (1) | DK1171665T3 (en) |
| ES (1) | ES2307516T3 (en) |
| NO (1) | NO329326B1 (en) |
| PT (1) | PT1171665E (en) |
| WO (1) | WO2000063488A1 (en) |
| ZA (1) | ZA200108552B (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104193705B (en) | 2008-07-16 | 2017-09-01 | 瑞恩麦特克斯股份有限公司 | The method for extracting furfural and glucose from biomass using one or more supercritical fluids |
| US8546560B2 (en) | 2008-07-16 | 2013-10-01 | Renmatix, Inc. | Solvo-thermal hydrolysis of cellulose |
| US8119823B2 (en) * | 2008-07-16 | 2012-02-21 | Renmatix, Inc. | Solvo-thermal hydrolysis of xylose |
| US8282738B2 (en) * | 2008-07-16 | 2012-10-09 | Renmatix, Inc. | Solvo-thermal fractionation of biomass |
| CN105525043B (en) | 2010-01-19 | 2021-03-19 | 瑞恩麦特克斯股份有限公司 | Production of fermentable sugars and lignin from biomass using supercritical fluids |
| KR101192576B1 (en) * | 2010-11-30 | 2012-10-17 | 코오롱인더스트리 주식회사 | Continuous Preparation Method for Furfural from Xylose |
| CN102228896B (en) * | 2011-04-01 | 2013-05-22 | 山东万盛环保科技发展有限公司 | Furfural slag recycling device |
| US8801859B2 (en) | 2011-05-04 | 2014-08-12 | Renmatix, Inc. | Self-cleaning apparatus and method for thick slurry pressure control |
| JP5967730B2 (en) | 2011-05-04 | 2016-08-10 | レンマティックス, インコーポレイテッドRenmatix, Inc. | Production of lignin from lignocellulosic biomass |
| CN103619827B (en) * | 2011-06-22 | 2016-08-24 | 巴斯夫欧洲公司 | Make the method that the compositions of carbohydrate containing is dehydrated |
| US8759498B2 (en) | 2011-12-30 | 2014-06-24 | Renmatix, Inc. | Compositions comprising lignin |
| US9174909B2 (en) | 2012-02-02 | 2015-11-03 | Wisconsin Alumni Research Foundation | Two-stage, acid-catalyzed conversion of carbohydrates into levulinic acid |
| CN103193737B (en) * | 2013-03-29 | 2015-01-28 | 山东龙力生物科技股份有限公司 | Method for preparing furfural and co-producing lignin and cellulosic ethanol via plant material |
| SG10202003336XA (en) | 2014-09-26 | 2020-05-28 | Renmatix Inc | Cellulose-containing compositions and methods of making same |
| EP3626711A1 (en) * | 2018-09-24 | 2020-03-25 | Arbaflame Technology AS | Process for the production of furfural |
| CN116144038B (en) * | 2022-11-02 | 2024-05-07 | 华南理工大学 | Method for preparing furfural, lignin sulfonate and high degradable cellulose by integrated multi-process coupling |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1838109A (en) | 1930-06-06 | 1931-12-29 | Brown Co | Production of furfural |
| FR1129139A (en) | 1955-07-15 | 1957-01-16 | Paper mill waste liquor treatment process | |
| US2845441A (en) | 1955-11-16 | 1958-07-29 | Brown Co | Processes for production of furfural |
| AT367473B (en) | 1980-04-10 | 1982-07-12 | Kanzler Walter | METHOD FOR OBTAINING FURFUROL, FORMIC, ACETIC ACID FROM ACID HYDROLYSATES OF PLANTS |
| AT376717B (en) | 1983-05-02 | 1984-12-27 | Chemiefaser Lenzing Ag | METHOD FOR OBTAINING FURFUROL FROM ACID WATER DRAINAGE OF THE CELLULAR EQUIPMENT AND SYSTEM FOR IMPLEMENTING THE METHOD |
| US4533743A (en) * | 1983-12-16 | 1985-08-06 | Atlantic Richfield Company | Furfural process |
-
1999
- 1999-04-16 DE DE19917178A patent/DE19917178A1/en not_active Withdrawn
-
2000
- 2000-04-14 EP EP00940001A patent/EP1171665B1/en not_active Expired - Lifetime
- 2000-04-14 CA CA002370561A patent/CA2370561C/en not_active Expired - Fee Related
- 2000-04-14 PT PT00940001T patent/PT1171665E/en unknown
- 2000-04-14 DK DK00940001T patent/DK1171665T3/en active
- 2000-04-14 ES ES00940001T patent/ES2307516T3/en not_active Expired - Lifetime
- 2000-04-14 AU AU54999/00A patent/AU5499900A/en not_active Abandoned
- 2000-04-14 AT AT00940001T patent/ATE404728T1/en active
- 2000-04-14 BR BRPI0009815-9A patent/BR0009815B1/en not_active IP Right Cessation
- 2000-04-14 US US09/958,936 patent/US6642396B1/en not_active Expired - Fee Related
- 2000-04-14 DE DE60039860T patent/DE60039860D1/en not_active Expired - Lifetime
- 2000-04-14 WO PCT/ZA2000/000072 patent/WO2000063488A1/en active Search and Examination
-
2001
- 2001-10-16 NO NO20015031A patent/NO329326B1/en not_active IP Right Cessation
- 2001-10-18 ZA ZA200108552A patent/ZA200108552B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| PT1171665E (en) | 2008-10-07 |
| EP1171665B1 (en) | 2008-08-13 |
| BR0009815A (en) | 2002-01-08 |
| CA2370561C (en) | 2009-06-16 |
| US6642396B1 (en) | 2003-11-04 |
| ES2307516T3 (en) | 2008-12-01 |
| AU5499900A (en) | 2000-11-02 |
| CA2370561A1 (en) | 2000-10-26 |
| DK1171665T3 (en) | 2008-12-15 |
| ATE404728T1 (en) | 2008-08-15 |
| BR0009815B1 (en) | 2011-03-22 |
| WO2000063488A1 (en) | 2000-10-26 |
| DE60039860D1 (en) | 2008-09-25 |
| EP1171665A1 (en) | 2002-01-16 |
| NO20015031D0 (en) | 2001-10-16 |
| ZA200108552B (en) | 2002-08-22 |
| DE19917178A1 (en) | 2000-10-19 |
| NO20015031L (en) | 2001-12-11 |
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